ISSN 2075-1133, Inorganic Materials: Applied Research, 2020, Vol. 11, No. 2, pp. 429–434. © Pleiades Publishing, Ltd.

, 2020.
Russian Text © The Author(s), 2019, published in Perspektivnye Materialy, 2019, No. 11, pp. 41–48.

GENERAL PURPOSE MATERIALS

Rheological Properties of Composites Based on Aluminum Hydroxide

and Low- and High-Density Polyethylene Blends
N. B. Arzumanovaa, *, F. A. Mustafayevaa, **, and N. T. Kakhramanova, ***
a
Institute of Polymer Materials, Azerbaijan National Academy of Sciences, Sumgait, AZ5004 Azerbaijan
*e-mail: arzumanova-nushaba@rambler.ru
**e-mail: mustafayevafatima@mail.ru
***e-mail: najaf1946@rambler.ru
Received January 21, 2019; revised March 14, 2019; accepted March 15, 2019

Abstract—The results of the study of the rheological characteristics of low- and high-density polyethylene
blend in the ratio of 50 : 50 and its composites filled with aluminum hydroxide are presented. The influence
of the concentration of aluminum hydroxide, temperature, and shear stress on the regularity of changes in the
effective viscosity and shear rate has been established. Rheograms of low- and high-density polyethylene
blend in the ratio of 50 : 50 and composites based on it are presented. The dependence of viscosity on tem-
perature in Arrhenius coordinates is determined, according to which the “apparent” activation energy of vis-
cous flow for the initial low- and high-density polyethylene blend and its composites filled with aluminum
hydroxide varies in the range of 6–19 and 11–31 kJ/mol, respectively. A universal temperature-invariant
characteristic of the viscosity properties of low-and high- density polyethylene blend in the ratio of 50 : 50 and
its composites filled with aluminum hydroxide, which makes it possible to predict the change in the melt vis-
cosity of composites in a wide range of shear rates and stresses, is drawn. It is shown that, with an increase in
the concentration of aluminum hydroxide in the polymer mixture to 5 wt %, the value of the shear rate
remains almost unchanged relative to the initial low- and high-density polyethylene blend (50/50). Rheolog-
ical studies of the melt of polymer materials have been carried out in accordance with the standard ASTM
D1238 on a CEAST MF50 capillary rheometer (INSTRON, Italy) in the temperature range of 190–250°C
and in the load range of 3.8–21.6 kg.

Keywords: rheology, shear stress, shear rate, polymer blends, aluminum hydroxide
DOI: 10.1134/S2075113320020045

INTRODUCTION hydroxides increase the thermal stability of polymer

Polyolefins are the largest representatives of syn-
thetic polymers according to overall production and
consumption. Several million tons of polyolefins are
produced and consumed every year all over the world.
Owing to their use in various fields of industry, rela-
tively low cost, and broad range of valuable properties,
they are widely used in the production of structural
products. These fields of application include automo-
tive and space engineering, packaging, medical prod-
ucts, consumer products, electronics, cable industry,
and construction.
However, insufficient thermal stability of these
materials is still a serious problem, which can restrict
their potential diverse application [1]. Moreover,
known and effective halogen-containing antipyrenes
are gradually being prohibited, because they are envi-
ronmentally toxic [2]. Thus, there are particular efforts
in the development of a new class of antipyrenes (fire
retardants) for polymer materials. Numerous studies
in this direction showed that amphoteric metal
materials; for this reason, they can be recommended
as potential environmentally safe antipyrenes [3–5].
In this work, we did not aim at the preparation of
nonflammable polymer material. It was interesting to
study the effect of small concentrations of aluminum
hydroxide (up to 5 wt %) on rheological features of the
composite melt on its basis, because there is a slight
worsening of stress–strain properties of the compos-
ites at the concentration of aluminum hydroxide
higher than 5 wt %.
The size and shape of filler particles and concen-
tration and degree of physicochemical interaction
with the polymer matrix are key factors. In addition,
rheological properties give important information
during evaluation of processability of composite mate-
rials [6]. However, detailed studies of rheological
behavior of molten polymer and their composite
blends are quite limited in the literature.
The aim of this work is to study the effect of con-
centration of filler, temperature, and shear stress on

429
430 ARZUMANOVA et al.

logJ (a) logJ (b)

4 4
3 3
2.0 2.0 2
2
1 1
1.5 1.5

1.0 1.0

0.5 0.5

0 0
3.5 4.0 4.5 logW 3.5 4.0 4.5 logW
(c) (d)
logJ logJ
4 4
3 3
2.0 2 2.0 2
1 1
1.5 1.5

1.0 1.0

0.5 0.5

0 0
3.5 4.0 4.5 logW 3.5 4.0 4.5 logW

Fig. 1. Dependence of shear rate on shear stress of (a) LDPE/HDPE (50/50), (b) LDPE/HDPE + 1 wt % Al(OH)3,
(c) LDPE/HDPE + 3 wt % Al(OH)3, and (d) LDPE/HDPE + 5 wt % Al(OH)3 at various temperatures, °C: (1) 190, (2) 210,
(3) 230, (4) 250.

rheological properties of initial blend of low- (LDPE)
and high-density (HDPE) polyethylene and filled
composites on its basis.
EXPERIMENTAL
LDPE and HDPE blends were used as the object of
study.
HDPE: density is 963 kg/m3, failure stress is 25 MPa,
and elongation is 500%; LDPE: density is 912 kg/m3,
failure stress is 10.5 MPa, and elongation is 250%.
Aluminum hydroxide Al(OH)3 is a colorless solid
insoluble in water; it possesses amphoteric properties
and is a component of many bauxites. Amorphous
aluminum hydroxide has a variable composition of
Al2O3 ⋅ nH2O. It decomposes upon heating to 180–
200°C. The filler particle size is 80–160 nm.
The polymer compositions based on LDPE/HDPE
and aluminum hydroxide blend were prepared during
mixing on roll mills at 170°C. The concentration of
aluminum hydroxide was 1–5 wt %.
The rheological properties of the melt of polymer
materials were measured according to [7] on a CEAST
MF50 capillary rheometer (INSTRON, Italy), which
determines the following properties: viscosity, shear
rate, and shear stress. The rheometer was equipped
with a nozzle with the length-to-diameter ratio of cap-
illary of 24. Measurements were carried out at four
temperatures (in the range from 190 to 250°C) and five
loads (from 3.8 to 21.6 kg), because according to
experimental statistics this is a minimum number of
experimental points which give a relevant statement
on the process or phenomenon [8].
RESULTS AND DISCUSSION
The particle size of aluminum hydroxide is 80–
160 nm, which is similar to nanoparticles to a certain
extent. For this reason, it was interesting to show how
relatively small concentrations of aluminum hydroxide
(up to 5 wt %) affect the mixing and the rheological
characteristics of the polymer blends based on
HDPE/LDPE. With an increase in the filler content,
the composites filled with aluminum hydroxide had an
extremely high viscosity and low fluidity, which had
an adverse effect on their processability through cast-
ing under pressure and extrusion.

INORGANIC MATERIALS: APPLIED RESEARCH Vol. 11 No. 2 2020

 RHEOLOGICAL PROPERTIES OF COMPOSITES BASED ON ALUMINUM HYDROXIDE 431

logK (a) logK (b)

3.0 3.0
1
1
2 2
2.5 3 2.5
3
4
4
2.0 2.0
0 0.5 1.0 1.5 2.0 logJ 0 0.5 1.0 1.5 2.0 logJ
logK (c) logK (c)

3.0 3.0
1 1
2 2
2.5 2.5
3
3
4 4

2.0 2.0
0 0.5 1.0 1.5 2.0 logJ 0 0.5 1.0 1.5 2.0 logJ

Fig. 2. Dependence of melt viscosity on shear rate of (a) LDPE/HDPE (50/50), (b) LDPE/HDPE + 1 wt % Al(OH)3,
(c) LDPE/HDPE + 3 wt % Al(OH)3, and (d) LDPE/HDPE + 5 wt % Al(OH)3 at various temperatures, °C: (1) 190, (2) 210,
(3) 230, (4) 250.

The rheological properties of the blend of initial
polyethylenes at an LDPE-to-HDPE ratio of 50 : 50
were studied for comparison and greater clarity. Figure 1
shows rheograms (flow curves) of the considered
polymer blend and composites on its basis. In particu-
lar, Fig. 1a show the flow curves of the HDPE/LDPE
blend at a 50 : 50 ratio. The choice of this ratio of the
blend components was due to the fact that their high-
est process miscibility and mutual dispersion ability is
achieved [9].
As follows from the rheograms in Fig. 1b–1d, the
flow curves are linear at low temperatures and the lin-
ear dependence of the shear rate on shear stress is vio-
lated at relatively high temperatures. It can be deter-
mined from comparative analysis of the flow curves
that there is melt flow, which is similar to the Newto-
nian principle, upon filling of the LDPE/HDPE poly-
mer blend with 1 wt % of aluminum hydroxide. How-
ever, with an increase in the filler content to 3–5 wt %,
the Newtonian principle of melt flow is violated.
There is a slight growth of the shear rate of the
composite melt only at the Al(OH)3 filler content of
1 wt % in the composite, while with a further increase
in the concentration of filler the shear rate approaches
the shear rate of initial LDPE/HDPE polymer blend.
Analysis of the flow curves showed that there is a
uniform increase in the shear rate of the composites
with an increase in temperature and shear stress,
which can presumably be caused by the stability and
controlling ability of heterogeneous nucleation cen-
ters, which are formed by filler particles in the melt. In
this case, thermal-fluctuation break and recovery of
agglomerates is controlled by heterogeneous centers.
It is evident that aluminum hydroxide is a strong het-
erogeneous nucleation center [10].
Another important characteristic of polymer mate-
rial is the effective viscosity of melt. Figures 2a–2d
show in logarithmic coordinates the dependence of
the effective viscosity of melt on the temperature and
shear rate of the LDPE/HDPE blend and its compos-
ites. Analysis of the curves in Fig. 2a shows that this
dependence is linear at 190°C; however, the linear
dependence is violated at 210–250°C and relatively
low shear rates.
Figures 2b–2d show the dependences of the viscos-
ity on the shear rate and temperature in the case of the
composites based on the LDPE/HDPE blend filled

INORGANIC MATERIALS: APPLIED RESEARCH Vol. 11 No. 2 2020

432 ARZUMANOVA et al.

logK (a) logK (b)

1
2 1
3 2
4 3
3.0 3.0
5 4
5

2.5 2.5

2.0 2.0
1.9 2.0 2.1 2.2 1.9 2.0 2.1 2.2
1/T, 103 K–1 1/T, 103 K–1
logK (c) logK (d)

1 1
2 2
3 3
3.0 4 3.0 4
5 5

2.5 2.5

2.0 2.0
1.9 2.0 2.1 2.2 1.9 2.0 2.1 2.2
1/T, 103 K–1 1/T, 103 K–1

Fig. 3. Dependence of melt viscosity on the inverse temperature of (a) LDPE/HDPE (50/50), (b) LDPE/HDPE + 1 wt %
Al(OH)3, (c) LDPE/HDPE + 3 wt % Al(OH)3, and (d) LDPE/HDPE + 5 wt % Al(OH)3 at different loads, kg: (1) 3.8, (2) 5.0,
(3) 10.0, (4) 12.5, (5) 21.6.

with aluminum hydroxide. Change in the viscosity
versus the shear rate and temperature in the case of
LDPE/HDPE + 1 wt % Al(OH)3 composite is almost
linear and some deviation from a linear dependence is
observed only at 250°C.
With an increase in temperature and shear rate,
there is a pseudoplastic flow, which is characterized by
a decrease in the viscosity of melt. This fact can be
interpreted by the distortion of dynamic equilibrium in
the change in the failure and recovery rate of macro-
molecule associates in melt. In this case, failure occurs
through individual displacement of segments as indi-
vidual kinetic units. It is possible that there is a partic-
ular orientation of macromolecular segments at shear
stress on the developed surface of filler particles,
which is accompanied by the formation of heteroge-
neous nucleation centers in melt.
The temperature of melt significantly affects the
process characteristics of polymer melts, thus deter-
mining the choice of processing mode, which posi-
tively affects the product quality obtained during pres-
sure casting and extrusion. According to Frenkel–
Eyring theory, viscosity exponentially depends on
temperature. The activation energy of viscous flow is
determined according to the dependence logη = f(1/T).
In the case of nonlinear dependence of the logarithm of
viscosity on inverse temperature, so-called apparent acti-
vation energy of flow is calculated [11, 12]. Figures 3a–3d
show the dependences of inverse temperature on the
effective viscosity of the LDPE/HDPE blend and the
composites on its basis in the broad loading range of
3.8 to 21.6 kg.
Figure 3a shows the dependences of the viscosity of
melt on inverse temperature in the case of LDPE/HDPE
polymer blend. Analysis of these curves shows that the
dependence of viscosity on temperature in the loading
range from 3.8 to 21.6 kg is mainly nonlinear, while the
apparent activation energy of viscous flow of this blend
varies in a rather broad range from 6.0 to 19.0 kJ/mol.
Figure 3b shows the dependences of the viscosity of
melt on inverse temperature in the case of
LDPE/HDPE + 1 wt % Al(OH)3 composite. It is evi-
dent from these curves that the dependences of viscos-
ity on temperature are linear at shear stresses of 3.8

INORGANIC MATERIALS: APPLIED RESEARCH Vol. 11 No. 2 2020

 RHEOLOGICAL PROPERTIES OF COMPOSITES BASED ON ALUMINUM HYDROXIDE
logK/K0
0 which gives flow curves on the basis of a minimum
–1
–2
3.5 4.0 4.5 5.0
logJ K0
Fig. 4. Temperature-invariant characteristic of viscosity
properties of LDPE/HDPE (50/50) blend and its alumi-
num hydroxide-filled composites.
and 5.0 kg, which gives the activation energy of viscous
flow of 11.0 kJ/mol. However, at shear stresses of
10.0–21.6 kg, the apparent activation energy of viscous
flow varies in the range of 11.0–22.0 kJ/mol.
Figures 3c and 3d show the dependences of logη =
f(1/T) for LDPE/HDPE + 3 wt % Al(OH)3 and
LDPE/HDPE + 5 wt % Al(OH)3 composites. It can
be determined from comparison of these curves that
the dependence of viscosity on temperature is a curve
in the range of non-Newtonian flow and the apparent
activation energy of viscous flow varies in the range of
13.0–31.0 kJ/mol. However, this dependence is linear in
the case of LDPE/HDPE + 5 wt % Al(OH)3 composite
and the activation energy corresponds to 11.0 kJ/mol.
It can be stated from the results of the study that the
activation energy of viscous flow of filled composites is
higher than that of the initial mixture. The flow of
polymer materials is featured by the fact that macro-
molecules cannot be displaced as a whole unit. As a
result, viscous flow deformation is carried out through
successive displacement of macromolecular segments
by “holes” (free volume). The segments of macro-
chains are not displaced to the neighboring position
when the total volume of all “holes” (free volume) in
the polymer is equal to or less than 2.5% of the total vol-
ume of polymer. Thus, the polymer flow is possible when
there is a sufficient amount of free volume in melt.
Disperse aluminum hydroxide particles restrict viscous
flow filling the free volume; for this reason, large activa-
tion energy is necessary for their displacement.
With the aim of further systematization and gener-
alization of experimental data, it was important to plot
the temperature-invariant characteristics of flow of
the composites. The method of universal tempera-
ture-invariant curve allows one to evaluate the state of
INORGANIC MATERIALS: APPLIED RESEARCH
433
polymer in a particular flow mode. This method also
significantly facilitates measurement of viscosity in a
broad range of stresses, shear rates, and temperatures,
amount of experimental data. This is particularly con-
venient when it is necessary to obtain approximate
characteristics of rheological properties under real
processing conditions of polymer. Figure 4 shows the
temperature-invariant characteristics of viscous char-
acteristics of the LDPE/HDPE blend and its composites
filled with aluminum hydroxide at 1, 3, and 5 wt %.
Analysis of the data in Fig. 4 shows that the reduced
viscosity ηe/η0, where η0 is the highest Newtonian vis-
cosity and ηe is the effective viscosity of melt, decreases
with an increase in the reduced shear rate γη0. Existence
of temperature-invariant characteristics of melt indi-
cates a qualitatively identical origin of break of the
associates in the viscous-flow state.
CONCLUSIONS
Flow curves and viscosity of the composites based
on high- and low-density polyethylene blends filled
with aluminum hydroxide have been studied. With an
increase in the concentration of aluminum hydroxide
to 5 wt %, the shear rate remains almost constant with
respect to the LDPE/HDPE (50 : 50) initial blend.
The dependence of viscosity on temperature has
been determined in Arrhenius coordinates, according
to which the apparent activation energy of viscous
flow of the LDPE/HDPE initial blend and its com-
posites with aluminum hydroxide varies in the ranges
of 6.0–19.0 and 11.0–31.0 kJ/mol, respectively.
A universal temperature-invariant characteristic of
viscosity has been plotted, which allows one to predict
the change in the viscosity of composite melt in a
broad range of shear rates and stresses.
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Translated by A. Muravev

SPELL: 1. OK

INORGANIC MATERIALS: APPLIED RESEARCH Vol. 11 No. 2 2020

CONDUCTIVE MATERIAL BASED ON COPPER POWDER WITH
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